Nickel cobalt complex hydroxide particles and method for producing the same, positive electrode active material for non-aqueous electrolyte secondary battery and method for producing the same, and non-aqueous electrolyte secondary battery

ABSTRACT

A method for producing a nickel cobalt complex hydroxide includes first crystallization of supplying a solution containing Ni, Co and Mn, a complex ion forming agent and a basic solution separately and simultaneously to one reaction vessel to obtain nickel cobalt complex hydroxide particles, and a second crystallization of, after the first crystallization, further supplying a solution containing nickel, cobalt, and manganese, a solution of a complex ion forming agent, a basic solution, and a solution containing said element M separately and simultaneously to the reaction vessel to crystallize a complex hydroxide particles containing nickel, cobalt, manganese and said element M on the nickel cobalt complex hydroxide particles crystallizing a complex hydroxide particles comprising Ni, Co, Mn and the element M on the nickel cobalt complex hydroxide particles.

CROSS REFERENCE TO RELATED APPLICATION

This is a divisional application of U.S. patent application Ser. No.15/139,903, filed Apr. 27, 2016, which claims priority under 35 U.S.C. §119 to Japanese Patent Application No. 2015-092102, filed Apr. 28, 2015and Japanese Patent Application No. 2016-079178, filed Apr. 11, 2016.

BACKGROUND Technical Field

The present disclosure relates to nickel cobalt complex hydroxideparticles which are raw materials of a positive electrode activematerial for non-aqueous electrolyte secondary battery and a method forproducing the same, a positive electrode active material for non-aqueouselectrolyte secondary battery for which the nickel cobalt complexhydroxide particles are raw materials and a method for producing thesame, and a non-aqueous electrolyte secondary battery for which thepositive electrode active material for non-aqueous electrolyte secondarybattery is used as a positive electrode material.

Description of Related Art

With miniaturization and increasing demand of electronic devices such asmobile phone and VTR in recent years, a secondary battery that is anelectric power source for these electronic devices is required to havehigher energy. A non-aqueous electrolyte secondary battery such aslithium ion secondary battery is expected to serve as such a secondarybattery. As a positive electrode active material for the lithium ionsecondary battery, one or more lithium transition metal complex oxideshaving a layered structure, such as lithium cobalt oxide, lithium nickeloxide, and lithium nickel cobalt manganese oxide have been used.

Patent Literature 1 (JP2008-305777A) describes a technique in which, inorder to suppress excessive grain growth and sintering duringcalcination, one or more additive agents are added in a range of 0.01mol % to less than 2 mol % with respect to the total molar amount oftransition metal elements in a raw material of a main component, then,calcination is carried out. With this technique, while obtainingsufficient crystallinity in the step of calcinating the active material,excessive growth of particles and excessive sintering can be suppressedby the additive elements on the surfaces of secondary particles, so thatfine particles can be obtained. The method described in PatentLiterature 1 (JP2008-305777A) includes pulverizing and mixing the rawmaterials of the main component simultaneously in a liquid medium, then,spray-drying the obtained slurry, followed by calcination.

On the other hand, there is a coprecipitation method as a method forproducing a nickel cobalt complex hydroxide particles which is aprecursor of lithium transition metal complex oxide and is used as a rawmaterial for the above-mentioned lithium transition metal complex oxide.

Patent Literature 2 describes that an additive element is coprecipitatedwith main component in a seed growth step or a particle growth step forobtaining a nickel cobalt manganese complex hydroxide particles so thatthe additive element is homogeneously distributed inside a secondaryparticles or covers the surface of the secondary particles.

CITATION LIST Patent Literature

-   Patent Literature 1: JP 2008-305777 A-   Patent Literature 2: JP 2012-254889 A

SUMMARY

The present disclosure provides a positive electrode active material fornon-aqueous electrolyte secondary battery having good low-temperatureoutput power characteristics and high discharge capacity, and a methodfor producing the same, and a nickel cobalt complex hydroxide which is araw material for the positive electrode active material, and a methodfor producing the same.

According to certain embodiments of the present disclosure, a method forproducing a nickel cobalt complex hydroxide represented by a formulaNi_(1-x-y)Co_(x)Mn_(y)M_(z)(OH)_(2+a) in which 0.10≤x≤0.35, 0<y≤0.35,0<z≤0.05, and 0≤a≤0.5, M is at least one element selected from a groupconsisting of Al, Mg, Ca, Ti, Zr, Nb, Ta, Cr, Mo, W, Fe, Cu, Si, Sn, Bi,Ga, Y, Sm, Er, Ce, Nd, La, Cd and Lu is provided. The method includes afirst crystallization and a second crystallization. The firstcrystallization includes supplying a solution containing nickel, cobaltand manganese, a solution of a complex ion forming agent, and a basicsolution, separately and simultaneously, to one reaction vessel toobtain nickel cobalt complex hydroxide particles.

The second crystallization includes, after the first crystallization,further supplying the solution containing nickel, cobalt, manganese, thesolution of the complex ion forming agent, the basic solution, and asolution containing the element M, separately and simultaneously to thereaction vessel to crystallize particles of complex hydroxide particlescontaining nickel, cobalt, manganese, and the element M on the complexhydroxide particles. Assuming that total molar amount of nickel, cobaltand manganese supplied in the step of first crystallization is MOL(1)and that total molar amount of nickel, cobalt and manganese supplied inthe step of second crystallization is MOL(2), MOL(1) and MOL(2) satisfyan inequality of 0.30≤MOL(1)/{MOL(1)+MOL(2)}<0.95.

According to certain embodiments of the present disclosure, a method forproducing a nickel cobalt complex hydroxide represented by a formula:Ni_(1-x)Co_(x)M_(z)(OH)_(2+a), in which 0.10≤x≤0.35, 0<z≤0.05, 0≤a≤0.5,M is at least one element selected from a group consisting of Al, Mg,Ca, Ti, Zr, Nb, Ta, Cr, Mo, W, Fe, Cu, Si, Sn, Bi, Ga, Y, Sm, Er, Ce,Nd, La, Cd and Lu is provided. The method includes a firstcrystallization and a second crystallization. The first crystallizationincludes supplying a solution containing nickel and cobalt, a solutionof a complex ion forming agent, and a basic solution, separately andsimultaneously to one reaction vessel to obtain nickel cobalt complexhydroxide particles.

The second crystallization includes, after the first crystallization,further supplying the solution containing nickel and cobalt, thesolution of the complex ion forming agent, the basic solution, and asolution containing the element M, separately and simultaneously to thereaction vessel to crystallize particles of complex hydroxide particlescontaining nickel, cobalt, manganese, and the element M on the complexhydroxide particles.

Assuming that total molar amount of nickel and cobalt supplied in thestep of first crystallization is MOL(1) and that total molar amount ofnickel and cobalt supplied in the step of second crystallization isMOL(2), MOL(1) and MOL(2) satisfy an inequality of0.30≤MOL(1)/{MOL(1)+MOL(2)}<0.95.

A nickel cobalt complex hydroxide according to certain embodiments ofthe present disclosure is represented by a formula:Ni_(1-x-y)Co_(x)Mn_(y)M_(z) (OH)_(2+a), in which 0.10≤x≤0.35, 0≤y≤0.35,0<z≤0.05, 0≤a≤0.5, M is at least one element selected from a groupconsisting of Al, Mg, Ca, Ti, Zr, Nb, Ta, Cr, Mo, W, Fe, Cu, Si, Sn, Bi,Ga, Y, Sm, Er, Ce, Nd, La, Cd and Lu. The nickel cobalt complexhydroxide is in a form of secondary particles formed by aggregation ofprimary particles. The secondary particles are made of a first layer, asecond layer, and a third layer. The first layer has a radial depthratio of less than 5% from a surface in the secondary particles. Thesecond layer has a radial depth ratio in a range of from 5% to less than50% and located at an inner side than the first layer in the secondaryparticles. The third layer has a radial depth ratio of 50% or greaterand located at an inner side than the second layer in the secondaryparticles. Further, a SEM-EDX spectrum of the element M with respect tothe radial depth in the secondary particles has a peak in the secondlayer.

A positive electrode active material according to certain embodiments ofthe present disclosure is a positive electrode active material fornon-aqueous electrolyte secondary battery comprising a lithiumtransition metal complex oxide represented by a formula:Li_(a)Ni_(1-x-y)Co_(x)Mn_(y)M_(z)O₂, in which 0.955≤a≤1.2, 0.10≤x0.35,0≤y≤0.35, 0<z≤0.05, M is at least one element selected from a groupconsisting of Al, Mg, Ca, Ti, Zr, Nb, Ta, Cr, Mo, W, Fe, Cu, Si, Sn, Bi,Ga, Y, Sm, Er, Ce, Nd, La, Cd and Lu. The lithium transition metalcomplex oxide is in a form of secondary particles formed by aggregationof primary particles. The secondary particles are made of a first layer,a second layer, and a third layer. The first layer has a radial depthratio of less than 5% from a surface in the secondary particles. Thesecond layer has a radial depth ratio of in a range of 5% to less than50% and at an inner side than the first layer in the secondaryparticles. The third layer has a radial depth ratio of 50% or greaterand located at an inner side than the second layer in the secondaryparticles. Further, a SEM-EDX spectrum of the element M with respect tothe depth of the secondary particles has a peak in the second layer.

A non-aqueous electrolytic solution secondary battery according tocertain embodiments of the present disclosure includes a positiveelectrode, a negative electrode, a separator, and a non-aqueouselectrolytic solution, in which the positive electrode includes thepositive electrode active material according to certain embodiments ofthe present disclosure.

A solid electrolyte secondary battery according to certain embodimentsof the present disclosure includes a positive electrode, a negativeelectrode, and a solid electrolyte, in which the positive electrodeincludes the positive electrode active material according to certainembodiments of the present disclosure.

According to the present disclosure, a positive electrode activematerial for non-aqueous electrolyte secondary battery and a nickelcobalt complex hydroxide which is a raw material for the positiveelectrode active material can be provided in an industrial scale.Moreover, with the use of the positive electrode active material, anon-aqueous electrolyte secondary battery that has batterycharacteristics of a high low-temperature output characteristics and ahigh discharge capacity can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an overview flow chart of steps for producing a positiveelectrode active material having a solid structure according to thepresent disclosure.

FIG. 2 is an overview flow chart of steps for producing a positiveelectrode active material having a hollow structure according to thepresent disclosure.

FIG. 3 is a SEM photograph (observation magnification of ×15,000) of anickel cobalt complex hydroxide of Example 1.

FIG. 4 is a cross-sectional SEM photograph of the nickel cobalt complexhydroxide of Example 1.

FIG. 5 is a CPS curve of the nickel cobalt complex hydroxide of Example1.

FIG. 6 is a SEM photograph (observation magnification of ×15,000) of alithium transition metal complex oxide of Example 1.

FIG. 7 is a cross-sectional SEM photograph of the lithium transitionmetal complex oxide of Example 1.

FIG. 8 is a CPS curve of the lithium transition metal complex oxide ofExample 1.

FIG. 9 is a cross-sectional SEM photograph of a nickel cobalt complexhydroxide of Comparative Example 1.

FIG. 10 is a CPS curve of the nickel cobalt complex hydroxide ofComparative Example 1.

FIG. 11 is a cross-sectional SEM photograph of a lithium transitionmetal complex oxide of Comparative Example 1.

FIG. 12 is a CPS curve of the lithium transition metal complex oxide ofComparative Example 1.

FIG. 13 is a cross-sectional SEM photograph of a nickel cobalt complexhydroxide of Comparative Example 2.

FIG. 14 is a CPS curve of the nickel cobalt complex hydroxide ofComparative Example 2.

FIG. 15 is a cross-sectional SEM photograph of a lithium transitionmetal complex oxide of Comparative Example 2.

FIG. 16 is a CPS curve of the lithium transition metal complex oxide ofComparative Example 2.

FIG. 17 is a cross-sectional SEM photograph of a nickel cobalt complexhydroxide of Example 2.

FIG. 18 is a CPS curve of the nickel cobalt complex hydroxide of Example2.

FIG. 19 is a cross-sectional SEM photograph of a lithium transitionmetal complex oxide of Example 2.

FIG. 20 is a CPS curve of the lithium transition metal complex oxide ofExample 2.

FIG. 21 is a cross-sectional SEM photograph of a nickel cobalt complexhydroxide of Example 3.

FIG. 22 is a CPS curve of the nickel cobalt complex hydroxide of Example3.

FIG. 23 is a cross-sectional SEM photograph of a lithium transitionmetal complex oxide of Example 3.

FIG. 24 is a CPS curve of the lithium transition metal complex oxide ofExample 3.

FIG. 25 is a cross-sectional SEM photograph of a nickel cobalt complexhydroxide of Example 4.

FIG. 26 is a CPS curve of the nickel cobalt complex hydroxide of Example4.

FIG. 27 is a cross-sectional SEM photograph of a lithium transitionmetal complex oxide of Example 4.

FIG. 28 is a CPS curve of the lithium transition metal complex oxide ofExample 4.

FIG. 29 is a cross-sectional SEM photograph of a nickel cobalt complexhydroxide of Comparative Example 3.

FIG. 30 is a CPS curve of the nickel cobalt complex hydroxide ofComparative Example 3.

FIG. 31 is a cross-sectional SEM photograph of a lithium transitionmetal complex oxide of Comparative Example 3.

FIG. 32 is a CPS curve of the lithium transition metal complex oxide ofComparative Example 3.

DETAILED DESCRIPTION OF EMBODIMENTS

The present disclosure relates to a nickel cobalt complex hydroxidewhich is a precursor of a positive electrode active material fornon-aqueous electrolyte secondary battery and a method for producing thesame as exemplified in FIG. 1 and FIG. 2. In addition, the presentdisclosure relates to a positive electrode active material fornon-aqueous electrolyte secondary battery for which the nickel cobaltcomplex hydroxide is used as a raw material and a method for producingthe same, and a non-aqueous electrolyte secondary battery in which thepositive electrode active material is used for a positive electrode.

Method of Producing Nickel Cobalt Complex Hydroxide Particles

The method for producing the nickel cobalt complex hydroxide accordingto the present disclosure is a method for producing the complexhydroxide by a crystallization reaction, the method can include a firstcrystallization in that a solution including nickel, cobalt andmanganese, a solution of a complex ion forming agent, and a basicsolution are supplied separately and simultaneously to one reactionvessel to obtain nickel cobalt complex hydroxide particles, and a secondcrystallization in that after the first crystallization, the solutioncontaining nickel, cobalt and manganese, the solution of the complex ionforming agent, the basic solution, and a solution containing the elementM are further separately and simultaneously supplied to the reactionvessel to crystallize complex hydroxide particles containing nickel,cobalt, manganese, and the element M on the nickel cobalt complexhydroxide particles. Alternatively, the method for producing the nickelcobalt complex hydroxide according to the present disclosure can includea first crystallization in that a solution containing nickel and cobalt,a solution of a complex ion forming agent, and a basic solution aresupplied separately and simultaneously to one reaction vessel to obtainnickel cobalt complex hydroxide particles and a second crystallizationin that after the first crystallization, the solution containing nickeland cobalt, the solution of the complex ion forming agent, the basicsolution, and a solution containing the element M are further separatelyand simultaneously supplied to the reaction vessel to crystallizecomplex hydroxide particles containing nickel, cobalt, and the element Mon the nickel cobalt complex hydroxide particles. Hereinafter, for easeof explanation, the solution containing nickel, cobalt and manganese andthe solution containing nickel and cobalt may be collectively simplyreferred to as “the solution such as the solution containing nickel,cobalt and manganese” or “mixed solution”.

Examples of a metal source for the solution such as the solutioncontaining nickel, cobalt and manganese include nitrates, sulfates,hydrochlorides, and the like. The solution such as the solutioncontaining nickel, cobalt and manganese is a mixed solution of aplurality of solutions each containing such a metal source with respectto the target. It is preferable that those solutions are adjusted to 25°C. or more.

In the case of mixing the solutions containing such metal sources toprepare the mixed solution, the concentration of the mixed solution ispreferably in a range of 1.0 to 2.6 mol/L, more preferably in a range of1.5 to 2.2 mol/L, as a total of the metal elements. In a case where theconcentration of the mixed solution is less than 1.0 mol/L, the amountof the crystallized substance per reaction vessel decreases, so that theproductivity may decrease. On the other hand, in a case where theconcentration of the mixed solution exceeds 2.6 mol/L, it exceeds asaturated concentration at room temperature and crystals arereprecipitated, resulting in a decrease in the concentration of thesolution.

Examples of the complex ion forming agent include acetic acid and citricacid which form a chelate complex with nickel, cobalt and manganese, inaddition to an ammonium ion supplying source. Examples of the basicsolution include sodium hydroxide solution.

Examples of a metal source of the element M include aluminum sulfate,sodium aluminate, aluminum nitrate, aluminum chloride, magnesiumsulfate, magnesium chloride, magnesium nitrate, magnesium perchlorate,calcium chloride, calcium nitrate, calcium perchlorate, barium chloride,barium nitrate, strontium chloride, strontium nitrate, titanyl sulfate,titanium potassium oxalate, zirconium sulfate, zirconium nitrate,zirconium oxychloride, niobium oxalate, niobium complex solution,tantalum complex solution, chromium sulfate, potassium chromate, sodiummolybdate, ammonium molybdate, sodium tungstate, ammonium tungstate,iron sulfate, iron chloride, iron nitrate, iron citrate, copper sulfate,copper nitrate, copper chloride, sodium silicate, tin sulfate, tinchloride, bismuth oxychloride, bismuth sulfate, gallium sulfate, galliumnitrate, gallium ammonium sulfate, yttrium sulfate, yttrium chloride,yttrium nitrate, samarium sulfate, samarium chloride, samarium nitrate,samarium oxalate, erbium sulfate, erbium chloride, erbium nitrate,cerium chloride, cerium ammonium nitrate, neodymium sulfate, neodymiumchloride, neodymium nitrate, lanthanum sulfate, lanthanum chloride,lanthanum nitrate, gadolinium sulfate, gadolinium chloride, gadoliniumnitrate, lutetium sulfate, lutetium chloride, and lutetium nitrate.

Forming Seed Crystals (Nuclei)

The method according to the present disclosure preferably includes astep of forming seed crystals before the step of first crystallization.FIG. 1 illustrates an example in which a pre-reaction solution used inthe step of forming seed crystals contains a complex ion forming agent.First, as a pre-reaction solution, a solution containing a complex ionforming agent and a basic solution are placed in the reaction vessel.Next, in the step of forming seed crystals, the mixed solution and thebasic solution are supplied in the pre-reaction solution to obtain thenickel cobalt complex hydroxide. In the present specification, the term“solution containing the complex ion forming agent” refers to, forexample, a solution having an ammonium ion concentration of 0.5% orgreater, in a case where the complex ion forming agent is ammonium ion,although the required amount varies depending on the type of the complexion forming agent.

FIG. 2 illustrates an example in which the pre-reaction solution used inthe step of forming seed crystals substantially does not contain anycomplex ion forming agent. First, a solution does not contain anycomplex ion forming agent and the basic solution are placed in thereaction vessel as the pre-reaction solution. Next, in the step offorming seed crystals, the mixed solution and the basic solution aresupplied in the pre-reaction solution to obtain the nickel cobaltcomplex hydroxide. In the present specification, the term “solutionsubstantially does not contain complex ion forming agent” refers to, forexample, in the case where the complex ion forming agent is ammoniumion, a solution having an ammonium ion concentration of 500 ppm or lessis preferable, and 100 ppm or less is further preferable, although therequired amount varies depending on the type of the complex ion formingagent.

In the step of forming seed crystals, for example, in a case where thecomplex ion forming agent is ammonium ion, the complex ion forming agentis preferably supplied so that 2000 ppm or greater of ammonium ion iscontained in a reaction liquid, although the required amount variesdepending on the type of the complex ion forming agent.

The step of forming seed crystals is preferably carried out withsolutions at 25° C. or greater and with supplying the basic solution sothat the pH value of the reaction solution at 25° C. to be in a range of9.5 to 12.0.

The crystallization time in the step of forming seed crystals isappropriately selected based on such as the particle diameter of thetarget nickel cobalt complex hydroxide, but the step of forming seedcrystals is preferably carried out in a time duration in the range of 20seconds to 10 minutes. In a case where the step of forming seed crystalsis carried out for less than 20 seconds, sufficient amount of seedcrystals cannot be formed. In a case where the step of forming seedcrystals exceeds 10 minutes, an excessive amount of the seed crystal areformed, which may aggregate and may results in variations in particlesize distribution.

After completing the step of forming seed crystals, it is preferable tostart the first crystallization after adjusting pH value of the solutionto a range of 9.5 to 12.0.

First Crystallization

In the step of first crystallization, the mixed solution, the solutionof the complex ion forming agent, and the basic solution are separatelyand simultaneously to the solution after completing the step of formingseed crystals to obtain the nickel cobalt complex hydroxide particles.

Supplying of the complex ion forming agent in the step of firstcrystallization is preferably carried out, for example, in the casewhere the complex ion forming agent is ammonium ion, so that 2000 ppm orgreater of the complex ion forming agent is contained in the reactionsolution, although the required amount varies depending on the type ofthe complex ion forming agent.

In the step of first crystallization, a liquid temperature of thesolution and pH value are preferably controlled such that the liquidtemperature of the solution is 25° C. or more and such that the pH valuemeasured on the basis of the liquid temperature of 25° C. is from 9.5 to12.0 by supplying the basic solution.

Second Crystallization

In the step of second crystallization, the nickel cobalt complexhydroxide particles can be obtained by supplying the mixed solution, thesolution containing the element M, the complex ion forming agent and thebasic solution to the solution after completing the step of firstcrystallization.

Supplying of the complex ion forming agent in the step of secondcrystallization is preferably carried out such that 2000 ppm or more ofthe complex ion forming agent is contained in the reaction liquid, forexample, in a case where the complex ion forming agent is ammonium ion,although the required amount varies depending on the type of the complexion forming agent.

Assuming that total molar amount of nickel, cobalt and manganesesupplied in the step of first crystallization is MOL(1) and that totalmolar amount of nickel, cobalt and manganese supplied in the step ofsecond crystallization is MOL(2) in a case of supplying the solutioncontaining nickel, cobalt and manganese, and assuming that total molaramount of nickel and cobalt supplied in the step of firstcrystallization is MOL(1) and that total molar amount of nickel andcobalt supplied in the step of second crystallization is MOL(2) in acase of supplying the solution containing nickel and cobalt, MOL(1) andMOL(2) satisfy an inequality of 0.30≤MOL(1)/{MOL(1)+MOL(2)}<0.95.Furthermore, MOL(1) and MOL(2) preferably satisfy an inequality of0.60≤MOL(1)/{MOL(1)+MOL(2)≤}0.90.

In a case where {MOL(1)/{MOL(1)+MOL(2)} is less than 0.3, thedistribution of the element M is homogeneous inside the secondaryparticles of the complex hydroxide. In a case where{MOL(1)/{MOL(1)+MOL(2)} is 0.95 or more, the element M is in a state ofcovering the surface.

The solution containing the element M may be mixed and supplied with themixed solution. However, the solution containing the element M ispreferably supplied separately. A supply rate during the step of secondcrystallization is set appropriately to be constant on the basis of thesupply volume and a time for the step of second crystallization.

Since the mixed solution and the solution containing the element M aresupplied simultaneously and coprecipitated in the step of secondcrystallization, the element M is relatively homogeneously dispersedinside the primary particles of the nickel cobalt complex hydroxideparticles obtained in the step of second crystallization. Also, theelement M is homogeneously dispersed inside a primary particles in apositive electrode active material for which the hydroxide is used as araw material. However, the element M is segregated outside the primaryparticles in a case where the nickel cobalt complex hydroxide and theelement M are dry-mixed or in a case where the nickel cobalt complexhydroxide is covered with the element M.

In the step of second crystallization, the solution is preferablycontrolled to have a liquid temperature of 25° C. or more and pH valueof from 9.5 to 12.0 measured on the basis of the liquid temperature of25° C. by use of the basic solution. The supplying of the basic solutionis carried out appropriately to maintain the pH value of the solutionwithin the range.

Crystallization time in the step of first crystallization and the stepof second crystallization are appropriately selected on the basis of aparticle diameter of the target complex hydroxide and the like. However,the crystallization time is preferably 3 hours or more in light ofcontrol of the particle diameter. In the case of less than 3 hours, thecontrol of the particle diameter is difficult since a time required forparticle growth is insufficient.

It is preferable to control an oxygen concentration within the reactionvessel to 10% by volume or less in the step of forming seed crystals,the step of first crystallization and the step of secondcrystallization.

Nickel Cobalt Complex Hydroxide

A composition of the nickel cobalt complex hydroxide according to thepresent disclosure is represented by a formula described below. Formula:Ni_(1-x-y)Co_(x)Mn_(y)M_(z)(OH)_(2+a), wherein 0.10≤x≤0.35, 0≤y≤0.35,0<z≤0.05, 0≤a≤0.5, M is at least one element selected from a groupconsisting of Al, Mg, Ca, Ti, Zr, Nb, Ta, Cr, Mo, W, Fe, Cu, Si, Sn, Bi,Ga, Y, Sm, Er, Ce, Nd, La, Cd and Lu.

The nickel cobalt complex hydroxide is in a shape of secondary particlesformed by aggregation of primary particles. The secondary particles aremade of a first layer having a radial depth ratio of less than 5% fromthe surface in the secondary particles, a second layer having a radialdepth ratio in a range of 5% to less than 50% and located at an innerside than the first layer in the secondary particles, and a third layerhaving a radial depth ratio of 50% or greater and located at an innerside than the second layer in the secondary particles. A SEM-EDXspectrum of the element M in the secondary particles in the depthdirection has a peak in the second layer. An accelerating voltage whenmeasuring the SEM-EDX is set to 10 kV.

The nickel cobalt complex hydroxide is dispersed in an epoxy resin andsolidified. Subsequently, a cross-section of the secondary particles isformed by a cross-section polisher. Distribution of the element M insidethe secondary particles can be determined by a line analysis of thecross-section with EDX.

When a CPS curve of the element M is determined by the line analysis, aspecific peak as described below appears.

In the present specification, “CPS curve” is a plot of a depth ratio inthe radial direction to the radius of the secondary particles of thenickel cobalt complex hydroxide on the horizontal axis and fluorescentX-ray intensity at that ratio (which indicates how much fluorescentX-ray having certain energy is detected, and is represented by a unit ofCPS) on the vertical axis. The CPS curve is usually represented as agraph connecting the plotted points. The fluorescent X-ray intensity isrepresented by relative difference from the intensity at a startingpoint for measuring the secondary particles assuming that the intensityat the starting point for measuring the secondary particles is zero.

The peak means a peak that includes a point of maximum coordinate valueon the vertical axis among peaks in the CPS curve.

Assuming that the amount of the element M in the first layer of thenickel cobalt complex hydroxide is S1, that the amount of the element Min the second layer is S2 and that the amount of the element M in thethird layer is S3, the amounts of S1, S2 and S3 can be evaluated asdescribed below.

The CPS curve shown in FIG. 5 and the like looks like a single curve.Actually, however, there are a number of plots. In the CPS curve, theproduct of a distance between each plot and a coordinate value on thevertical axis is determined as an area between each plot. An averagevalue of an area between each plot corresponding to the first layer isdefined as S1, an average value of an area between each plotcorresponding to the second layer is defined as S2 and an average valueof an area between each plot corresponding to the third layer is definedas S3.

The relation between the S1 and the S2 preferably satisfies aninequality of S2>1.02 S1. In the case of S2<1.02 Si, a distribution ofthe element M in the first layer and the second layer of the complexhydroxide is homogeneous or the element M is more distributed in thefirst layer.

The relation between the S2 and the S3 preferably satisfies aninequality of S2>1.02 S3. In the case of S2<1.02 S3, a distribution ofthe element M in the second layer and the third layer of the complexhydroxide is homogeneous, or the element M is more distributed in thethird layer.

An average particle diameter of the secondary particles of the nickelcobalt complex hydroxide is preferably adjusted to from 1 to 20 μm.Furthermore, the average particle diameter is preferably adjusted tofrom 2 to 7 μm. The value of the average particle diameter is adjustedby the total of the molar amounts (MOL(1)+MOL(2)) in the step of firstcrystallization and the step of second crystallization.

The average particle diameter of the secondary particles and the shapeand the average particle diameter of the primary particles of the nickelcobalt complex hydroxide can be confirmed by observation of the nickelcobalt complex hydroxide with SEM. Furthermore, the structure inside thesecondary particles of the nickel cobalt complex hydroxide can beconfirmed by observation of the secondary particles of the nickel cobaltcomplex hydroxide with cross-sectional SEM.

In the case where the pre-reaction solution substantially does notcontain the complex ion forming agent in the step of forming seedcrystals, a secondary particles of a nickel cobalt complex hydroxideobtained after the step of second crystallization has an inner core partcomprising a fine primary particles having an average particle diameterof from 0.01 to 0.3 μm. The secondary particles also has an outer shellpart outside the inner core part, the outer shell part comprisingplate-like or needle-like primary particles larger than the fine primaryparticles and having an average particle diameter of from 0.5 to 2 μm.Furthermore, a lithium transition metal oxide for which the nickelcobalt complex hydroxide is used as a raw material has a hollowstructure.

In a case where the pre-reaction solution contains the complex ionforming agent in the step of forming seed crystals, a secondaryparticles of a nickel cobalt complex hydroxide obtained after the stepof second crystallization consists of a rod-like or plate-like primaryparticles having an average particle diameter of from 0.3 to 3 μm asexemplified in FIG. 3. In addition, the inside of the secondaryparticles is dense as exemplified in FIG. 4. Furthermore, a lithiumtransition metal oxide for which the nickel cobalt complex hydroxide isused as a raw material has a solid structure as exemplified in FIG. 7.

In a case where a lithium transition metal oxide is obtained by use ofthe nickel cobalt complex hydroxide as a raw material, composition ratio(Ni:Mn:Co:M) of this complex hydroxide is approximately coincident withcomposition ratio of the obtained lithium transition metal oxide.

Method for Producing Positive Electrode Active Material for Non-AqueousElectrolyte Secondary Battery

Moisture contained in the nickel cobalt complex hydroxide can be removedand a nickel cobalt transition metal oxide can be obtained by a heattreatment of the nickel cobalt complex hydroxide under an air atmosphere(see the heat treating in the flowchart of FIG. 1 or FIG. 2). The heattreatment is preferably carried out at a temperature of from 105 to 900°C., further preferably from 250° C. to 650° C. Time for the heattreatment is preferably from 5 to 30 hours, further preferably from 10to 20 hours.

In the step of mixing in the flowchart of FIG. 1 or 2, the nickel cobalttransition metal oxide and a lithium compound are mixed to obtain amixture containing lithium.

A known mixing method can be used as appropriate. For example,dry-mixing the starting raw material using an agitation mixing machineor the like, or preparing a slurry of starting raw materials andwet-mixing using a mixer such as ball mill or the like. For the lithiumcompound, for example, lithium hydroxide, lithium nitrate, lithiumcarbonate, or a mixture of those can be used.

A ratio of the total of molar amounts of metals other than lithium tothe molar amount of lithium in the lithium mixture is preferably in arange of 0.95 to 1.20. In the case of the ratio less than 0.95,formation of by-product is observed. In the case of the ratio exceeding1.3, alkaline component is increased on the surface, and moistureadsorption due to deliquescent property of the alkaline component isobserved, resulting in poor handling ability.

A calcination step shown in FIG. 1 or 2 is a step for calcining thelithium mixture obtained in the mixing step to obtain a lithiumtransition metal complex oxide. The lithium transition metal complexoxide can be obtained by diffusion of lithium in the lithium compoundinto the nickel cobalt transition metal oxide in the calcination step.

Calcination is preferably carried out at a temperature from 700 to 1100°C. The calcination temperature is further preferably from 750 to 1000°C. In the case of the calcination temperature of less than 700° C.,diffusion of lithium is insufficient. In the case of the calcinationtemperature exceeding 1100° C., diffusion of the element M occurs, andthe distribution of the element M inside the secondary particles ishomogeneous. Calcination time of 10 hours or more is sufficient as atime to maintain a maximum temperature.

Calcination is preferably carried out in an oxidizing atmosphere, morepreferably an atmosphere containing from 10 to 100% by volume of oxygen.

After the calcination, a treatment such as cracking, pulverizing anddry-sieving of the lithium transition metal oxide is carried out asnecessary to obtain a positive electrode active material according tothe present disclosure.

Positive Electrode Active Material for Non-Aqueous Electrolyte SecondaryBattery

A positive electrode active material according to the present disclosurecomprises a lithium transition metal complex oxide represented by aformula: Li_(a)Ni_(1-x-y)Co_(x)Mn_(y)M_(z)O₂, wherein 0.955≤a≤1.2,0.10≤x≤0.35, 0≤y≤0.35, 0<z≤0.05, M is at least one element selected froma group consisting of Al, Mg, Ca, Ti, Zr, Nb, Ta, Cr, Mo, W, Fe, Cu, Si,Sn, Bi, Ga, Y, Sm, Er, Ce, Nd, La, Cd, Lu. The lithium transition metalcomplex oxide has hexagonal crystal structure having a layeredstructure.

The range of “a” for lithium is from 0.95 to 1.2 in the lithiumtransition metal oxide according to the present disclosure. In a casewhere “a” is less than 0.95, an interfacial resistance is increasedwhich generates at an interface between a surface of a positiveelectrode and an electrolyte in a non-aqueous electrolyte secondarybattery for which the positive electrode active material comprising theobtained lithium transition metal oxide is used, and thus, output powerof the battery is decreased. On the other hand, in a case where “a”exceeds 1.2, initial discharge capacity is reduced when the positiveelectrode active material is used in the positive electrode of thebattery.

The values of “x” and “y” are determined with taking into considerationthe charge and discharge capacity, cycle characteristics, safety and thelike of a non-aqueous electrolyte secondary battery for which thepositive electrode active material comprising the obtained lithiumtransition metal oxide is used. The value of “x” is in a range of 0.10to 0.35, the value of “y” is in a range of 0 to 0.35, preferably in arange of 0.10 to 0.35, and the value of “z” is in a range of 0.05 orless, preferably in a range of 0.02 or less.

In a case where the range of “z” for the element M exceeds 0.05, thecharge and discharge capacities are reduced due to the decreased amountof metal element contributing a reduction reaction.

The lithium transition metal complex oxide is in a form of secondaryparticles formed by aggregation of primary particles. The secondaryparticles are made of a first layer having a radial depth ratio of lessthan 5% from the surface in the secondary particles, a second layerhaving a radial depth ratio in a range of 5% to less than 50% andlocated at an inner side than the first layer in the secondaryparticles, and a third layer having a radial depth ratio of 50% or moreand located at an inner side than the second layer in the secondaryparticles. A SEM-EDX spectrum of the element M in the depth direction inthe secondary particles has a peak in the second layer. An acceleratingvoltage when measuring the SEM-EDX is set to 10 kV.

The lithium transition metal complex oxide is dispersed in an epoxyresin and solidified. Then, a cross-section of the secondary particlesis formed by using a cross-section polisher. Distribution of the elementM inside the secondary particles can be determined by using the lineanalysis of this cross-section with EDX.

When a CPS curve of the element M is determined by the line analysis, aspecific peak as described below usually appears. In the presentspecification, “CPS curve of a complex oxide” is a plot of a depth ratioin the radial direction to a radius of the secondary particles of thelithium transition metal complex oxide on the horizontal axis andfluorescent X-ray intensity along the radius on the vertical axis, andusually represented as a graph connecting the plotted points. Thefluorescent X-ray intensity is represented by relative difference fromthe intensity at a starting point for measuring the secondary particlesassuming that intensity at a starting point for measuring the particlesis zero.

The peak means a peak comprising a point of maximum coordinate value ofthe vertical axis among peaks comprised in the CPS curve of the complexoxide.

Assuming that the amount of the element M in the first layer of thelithium transition metal complex oxide is S4, that the amount of theelement M in the second layer is S5, and that the amount of the elementM in the third layer is S6, the amounts of S4, S5 and S6 can beevaluated as described below.

The CPS curve of the complex oxide shown in FIG. 5 and the like lookslike a single curve. Actually, however, there are a number of plots. Inthe CPS curve of the complex oxide, the product of a distance betweeneach plot and a coordinate value of the vertical axis is determined asan area between each plot. An average value of an area between each plotcorresponding to the first layer is defined as S4, an average value ofan area between each plot corresponding to the second layer is definedas S5 and an average value of an area between each plot corresponding tothe third layer is defined as S6.

The relation between the S4 and the S5 preferably satisfies aninequality of S5>1.02 S4. In the case of S5<1.02 S4, a distribution ofthe element M in the first layer and the second layer of the complexoxide particles is homogeneous or the element M is more distributed inthe first layer.

The relation between the S5 and the S6 preferably satisfies aninequality of S5>1.02 S6. In the case of S5<1.02 S6, the distribution ofthe element M in the second layer and the third layer of the complexoxide particles is homogeneous, or the element M is more distributed inthe third layer.

Since the element M is homogeneously dispersed inside the primaryparticles of the nickel cobalt complex hydroxide, the element M is alsohomogeneously dispersed inside the primary particles in the positiveelectrode active material for which the nickel cobalt manganese complexhydroxide particles is used. On the other hand, in a case where thenickel cobalt complex hydroxide and the element M are dry-mixed or in acase where the primary particles is covered with the element M, theelement M is not dispersed homogeneously inside the primary particles,but the element M is segregated outside the primary particles.

The secondary particles of the lithium transition metal complex oxidepreferably has an average particle diameter in a range of 1 to 20 μm. Astructure inside the secondary particles may be a hollow structurecomprising a hollow part in the third layer, or it may also be a solidstructure as exemplified in FIG. 7.

Hereinafter, more specific examples will be described in Examples.

Example 1 Production of Nickel Cobalt Complex Hydroxide

A nickel cobalt complex hydroxide is prepared in a manner shown below.

Forming Seed Crystals

First, the pre-reaction solution is prepared by putting water of up to10 kg into a reaction vessel, and adding aqueous ammonia with stirringto adjust ammonium ion concentration to be 1.8% by mass. The temperaturewithin the vessel is set to 25° C., and nitrogen gas is circulated inthe reaction vessel to maintain oxygen concentration in a space insidethe reaction vessel to 10% or less. 25% by mass of sodium hydroxidesolution is added to the water in the reaction vessel to adjust pH valueof the solution in the vessel to a range of 9.5 to 12.0.

Next, a nickel sulfate solution, a cobalt sulfate solution, and amanganese sulfate solution are mixed to obtain a mixed solution, inwhich a molar ratio of the metal elements is 1:1:1.

While controlling pH value in the reaction solution to a range of 9.5 to12.0 with a sodium hydroxide solution, the mixed solution is added tothe reaction vessel so that the reaction solution contains a solute of 4mol.

First Crystallization

The temperature within the vessel is maintained to 25° C. or more untilthe step of forming seed crystals is completed. The mixed solution in anamount corresponding to the solute of 770 mol and aqueous ammonia areadded simultaneously to the reaction vessel such that ammonium ionconcentration in the solution is 2000 ppm or more to carry out the stepof first crystallization while supplying a sodium hydroxide solution tocontrol pH value in the reaction solution to a range of from 9.5 to12.0.

Second Crystallization

After the step of first crystallization, the temperature within thevessel is maintained to 25° C. or more until the step of secondcrystallization is completed. The mixed solution in an amountcorresponding to the solute of 430 mol, an ammonium tungstate solutioncontaining tungsten equivalent to 12 mol and aqueous ammonia are addedsimultaneously to the reaction vessel such that ammonium ionconcentration in the solution is 2000 ppm or more to carry out the stepof second crystallization while supplying a sodium hydroxide solution tocontrol pH value in the reaction solution to a range of 9.5 to 12.0.Then, the product can be washed with water, filtrated and dried toobtain a complex hydroxide.

Analysis of Nickel Cobalt Complex Hydroxide

It is possible to confirm that a composition of the nickel cobaltcomplex hydroxide is Ni_(0.33)Co_(0.33)Mn_(0.33)W_(0.01)(OH)_(2+a),wherein 0≤a≤0.5 by dissolving its sample with an inorganic acid and thencarrying out a chemical analysis by ICP emission spectrometry.

From a SEM observation (magnification of ×15,000) of the nickel cobaltcomplex hydroxide, rod-like or plate-like primary particles having anaverage particle diameter in a range of 0.5 to 1.5 μm can be confirmedas exemplified in FIG. 3. Also, it is possible to confirm that thesecondary particles has an average particle diameter of 5 μm.

The nickel cobalt complex hydroxide is dispersed in an epoxy resin andsolidified. Then, a cross-section of the secondary particles is formedby using a cross-section polisher (manufactured by JEOL Ltd., Japan).

It is possible to confirm that the inside of the secondary particles isdense as exemplified in FIG. 4 by SEM observation of the cross-section.

It is possible to confirm a peak in the second layer from the obtainedCPS curve as exemplified in FIG. 5 by the line analysis of thecross-section with an energy dispersive X-ray analyzer EDX.

It is possible to confirm that S1 and S2 satisfy an inequality ofS2>1.02 Si from the CPS curve since S2 is 1.83 and S1 is 0.76.

It is possible to confirm that S2 and S3 satisfy an inequality ofS2>1.02 S3 from the CPS curve since S3 is 0.

Production of Positive Electrode Active Material

The nickel cobalt complex hydroxide is heat-treated at 300° C. for 20hours under an air (oxygen: 21% by volume) atmosphere, and is retrievedas a nickel cobalt transition metal complex oxide. Next, the nickelcobalt transition metal complex oxide is mixed with lithium carbonatesuch that a molar ratio of lithium carbonate to the nickel cobalttransition metal complex oxide is 1.15-fold, and the mixture is calcinedat 960° C. for 15 hours in an air atmosphere. After calcination, adispersion treatment is carried out, so that a positive electrode activematerial comprising lithium transition metal complex oxide can beobtained.

Analysis of Lithium Transition Metal Complex Oxide

It is possible to confirm that a composition of the lithium transitionmetal complex oxide is Li_(1.15)Ni_(0.33)Co_(0.33)Mn_(0.33)W_(0.01)O₂ bydissolving its sample with an inorganic acid and then carrying out achemical analysis by ICP emission spectrometry.

It is possible to confirm that a plurality of rod-like or plate-likeprimary particles having an average particle diameter of from 0.3 to 2.0μm aggregates into a secondary particles having an average particlediameter of 5 μm as exemplified in FIG. 6 by SEM observation(magnification of ×15000) of the lithium transition metal complex oxide.

The lithium transition metal complex oxide is dispersed in an epoxyresin and solidified, and then, a cross-section of the secondaryparticles is formed by the cross-section polisher (manufactured by JEOLLtd., Japan).

It is possible to confirm that the secondary particles has a solidstructure as exemplified in FIG. 7 by SEM observation of thecross-section.

It is possible to confirm a peak at the second layer from the obtainedCPS curve of the complex oxide as exemplified in FIG. 8 by the lineanalysis of the cross-section with the energy dispersive X-ray analyzerEDX.

It is possible to confirm that S4 and S5 satisfy an inequality ofS5>1.02 S4 from the CPS curve of the complex oxide since S5 is 0.657 andS4 is 0.0018.

It is possible to confirm that S2 and S3 satisfy an inequality ofS2>1.02 S3 from the CPS curve of the complex oxide since S6 is 0.60.

Comparative Example 1

Production of Nickel Cobalt Complex Hydroxide

Forming Seed Crystals

The step of forming seed crystals is carried out under a conditionsimilar to that in Example 1.

First Crystallization

The step of first crystallization is not carried out.

Second Crystallization

After the step of forming seed crystals, a temperature within the vesselis maintained to 25° C. or more until the step of second crystallizationis completed. The mixed solution in an amount corresponding to thesolute of 1200 mol, an ammonium tungstate solution containing tungstenequivalent to 12 mol and aqueous ammonia are added simultaneously to thereaction vessel such that ammonium ion concentration in the solution is2000 ppm or more to carry out the step of second crystallization whilesupplying a sodium hydroxide solution to control pH value in thereaction solution to a range of from 9.5 to 12.0. Then, the product canbe washed with water, filtrated and dried to obtain a complex hydroxide.

Analysis of Complex Hydroxide

It is possible to confirm that a composition of the complex hydroxide isNi_(0.33)Co_(0.33)Mn_(0.33)W_(0.01)(OH)_(2+a), wherein 0≤a≤0.5 by thechemical analysis in a similar manner to that in Example 1.

A cross-section of the secondary particles of the complex hydroxide isexposed in a similar manner to that in Example 1.

It is possible to confirm that the inside of the secondary particles isdense as exemplified in FIG. 9 by SEM observation of the cross-section.

It is possible to confirm a peak at the third layer from the obtainedCPS curve as exemplified in FIG. 10 by the line analysis with EDX in asimilar manner to that in Example 1.

It is possible to confirm that S1 and S2 satisfy an inequality ofS2>1.02 S1 from the CPS curve since S2 is 11.12 and S1 is 1.04.

It is possible to confirm that S2 and S3 satisfy an inequality of S2<S3from the CPS curve since S3 is 17.4.

Production of Positive Electrode Active Material

The step of forming seed crystals is carried out under a conditionsimilar to that in Example 1.

Analysis of Lithium Transition Metal Complex Oxide

It is possible to confirm that a composition of the lithium transitionmetal complex oxide is Li_(1.15)Ni_(0.33)Co_(0.33)Mn_(0.33)W_(0.01)O₂ bythe chemical analysis in a similar manner to that in Example 1.

A cross-section of the secondary particles of the lithium transitionmetal complex oxide is exposed under a condition similar to that inExample 1.

It is possible to confirm that the secondary particles has a solidstructure as exemplified in FIG. 11 by SEM observation of thecross-section.

A line analysis using EDX is performed in a similar manner as in Example1, and It is confirmed that a peak at the third layer from the obtainedCPS curve as exemplified in FIG. 12 by the line analysis with EDX in asimilar manner to that in Example 1.

It is possible to confirm that S4 and S5 satisfy an inequality ofS5>1.02 S4 from the CPS curve of the complex oxide since S5 is 1.34 andS4 is 0.45.

It is possible to confirm that S5 and S6 satisfy an inequality of S5<S6from the CPS curve since S6 is 1.95.

Comparative Example 2 Production of Nickel Cobalt Complex Hydroxide

A complex hydroxide is prepared in a manner shown below.

Forming Seed Crystals

The step of forming seed crystals is carried out under a conditionsimilar to that in Example 1.

First Crystallization

After the step of forming seed crystals, a temperature within the vesselis maintained to 25° C. or more until the step of second crystallizationis completed. The mixed solution in an amount corresponding to thesolute of 200 mol and aqueous ammonia are added simultaneously to thereaction vessel such that the ammonium ion concentration in the solutionis 2000 ppm or more to carry out the step of first crystallization whilesupplying a sodium hydroxide solution to control pH value in thereaction solution to a range of from 9.5 to 12.0.

Second Crystallization

After the step of first crystallization, the temperature within thevessel is maintained to 25° C. or more. The mixed solution in an amountcorresponding to the solute of 1000 mol, an ammonium tungstate solutioncontaining tungsten equivalent to 12 mol and aqueous ammonia are addedsimultaneously to the reaction vessel such that the ammonium ionconcentration in the solution is 2000 ppm or more to carry out the stepof second crystallization while supplying a sodium hydroxide solution tocontrol pH value in the reaction solution to a range of 9.5 to 12.0.Then, the product can be washed with water, filtrated and dried toobtain a complex hydroxide.

Analysis of Nickel Cobalt Complex Hydroxide

It is possible to confirm that a composition of the complex hydroxide isNi_(0.33)Co_(0.33)Mn_(0.33)W_(0.01)(OH)_(2+a), wherein 0≤a≤0.5 by thechemical analysis in a similar manner to that in Example 1.

A cross-section of the secondary particles of the nickel cobalt complexhydroxide is exposed in a similar condition to that in Example 1.

It is possible to confirm that the inside of the secondary particles isdense as exemplified in FIG. 13 by SEM observation of the cross-section.

It is possible to confirm a peak at the third layer from the obtainedCPS curve as exemplified in FIG. 14 by the line analysis with EDX in asimilar manner to that in Example 1.

It is possible to confirm that S1 and S2 satisfy an inequality ofS2>1.02 Si from the CPS curve since S2 is 3.09 and S1 is 0.32.

It is possible to confirm that S2 and S3 satisfy an inequality of S2<S3from the CPS curve since S3 is 3.74.

Production of Positive Electrode Active Material

Preparation is carried out under a condition similar to that in Example1.

Analysis of Lithium Transition Metal Complex Oxide

It is possible to confirm that a composition of the lithium transitionmetal complex oxide is Li_(1.15)Ni_(0.33)Co_(0.33)Mn_(0.33)W_(0.01)O₂ bythe chemical analysis in a similar manner to that in Example 1.

A cross-section of the secondary particles of the lithium transitionmetal complex oxide is exposed under a condition similar to that inExample 1.

It is possible to confirm the secondary particles has a solid structureas exemplified in FIG. 15 by SEM observation of the cross-section.

It is possible to confirm a peak at the third layer from the obtainedCPS curve as exemplified in FIG. 16 by the line analysis with EDX in asimilar manner to that in Example 1.

It is possible to confirm that S4 and S5 satisfy an inequality ofS5>1.02 S4 from the CPS curve of the complex oxide since S5 is 3.58 andS4 is 0.35.

It is possible to confirm that S5 and S6 satisfy an inequality of S5<S6from the CPS curve since S6 is 5.14.

Example 2 Production of Nickel Cobalt Complex Hydroxide

A complex hydroxide is prepared in a manner shown below.

Forming Seed Crystals

The step of forming seed crystals is carried out under a conditionsimilar to that in Example 1.

First Crystallization

A temperature within the vessel is maintained to 25° C. or more untilthe step of forming seed crystals is completed. The mixed solution in anamount corresponding to the solute of 600 mol and aqueous ammonia areadded simultaneously to the reaction vessel such that the ammonium ionconcentration in the solution is 2000 ppm or more to carry out the stepof first crystallization while supplying a sodium hydroxide solution tocontrol pH value in the reaction solution to a range of 9.5 to 12.0.

Second Crystallization

After the step of first crystallization, the temperature within thevessel is maintained to 25° C. or more until the step of secondcrystallization is completed. The mixed solution in an amountcorresponding to the solute of 600 mol, an ammonium tungstate solutioncontaining tungsten equivalent to 12 mol and aqueous ammonia are addedsimultaneously to the reaction vessel such that the ammonium ionconcentration in the solution is 2000 ppm or more to carry out the stepof second crystallization while supplying a sodium hydroxide solution tocontrol pH value in the reaction solution to a range of 9.5 to 12.0.Then, the product can be washed with water, filtrated and dried toobtain a complex hydroxide.

Analysis of Nickel Cobalt Complex Hydroxide

It is possible to confirm that a composition of the complex hydroxide isNi_(0.33)Co_(0.33)Mn_(0.33)W_(0.01)(OH)_(2+a), wherein 0≤a≤0.5 by thechemical analysis in a similar manner to that in Example 1.

A cross-section of the secondary particles of the nickel cobalt complexhydroxide is exposed in a similar condition to that in Example 1.

It is possible to confirm that the inside of the secondary particles isdense as exemplified in FIG. 17 by SEM observation of the cross-section.

It is possible to confirm a peak at the second layer from the obtainedCPS curve as exemplified in FIG. 18 by the line analysis with EDX in asimilar manner to that in Example 1.

It is possible to confirm that S1 and S2 satisfy an inequality ofS2>1.02 S1 from the CPS curve since S2 is 2.78 and S1 is 1.50.

It is possible to confirm that S2 and S3 satisfy an inequality ofS2>1.02 S3 from the CPS curve since S3 is 0.

Production of Positive Electrode Active Material

Preparation is carried out under a condition similar to that in Example1.

Analysis of Lithium Transition Metal Complex Oxide

It is possible to confirm that a composition of the lithium transitionmetal complex oxide is Li_(1.15)Ni_(0.33)Co_(0.33)Mn_(0.33)W_(0.01)O₂ bythe chemical analysis in a similar manner to that in Example 1.

A cross-section of the secondary particles of the lithium transitionmetal complex oxide is exposed under a condition similar to that inExample 1.

It is possible to confirm the secondary particles has a solid structureas exemplified in FIG. 19 by SEM observation of the cross-section.

It is possible to confirm a peak at the second layer from the obtainedCPS curve as exemplified in FIG. 20 by the line analysis with EDX in asimilar manner to that in Example 1.

It is possible to confirm that S4 and S5 satisfy an inequality ofS5>1.02 S4 from the CPS curve of the complex oxide since S5 is 2.24 andS4 is 1.49.

It is possible to confirm that S5 and S6 satisfy an inequality ofS5>1.02 S6 from the CPS curve of the complex oxide since S6 is 0.75.

Example 3 Production of Nickel Cobalt Complex Hydroxide

A complex hydroxide is prepared in a manner shown below.

Forming Seed Crystals

The step of forming seed crystals is carried out under a conditionsimilar to that in Example 1.

First Crystallization

A temperature within the vessel is maintained to 25° C. or more untilthe step of forming seed crystals is completed. The mixed solution in anamount corresponding to the solute of 1104 mol and aqueous ammonia areadded simultaneously to the reaction vessel such that the ammonium ionconcentration in the solution is 2000 ppm or more to carry out the stepof first crystallization while supplying a sodium hydroxide solution tocontrol pH value in the reaction solution to a range of 9.5 to 12.0.

Second Crystallization

After the step of first crystallization, the temperature within thevessel is maintained to 25° C. or more until the step of secondcrystallization is completed. The mixed solution in an amountcorresponding to the solute of 96 mol, an ammonium tungstate solutioncontaining tungsten equivalent to 6 mol and aqueous ammonia are addedsimultaneously to the reaction vessel such that the ammonium ionconcentration in the solution is 2000 ppm or more to carry out the stepof second crystallization while supplying a sodium hydroxide solution tocontrol pH value in the reaction solution to a range of from 9.5 to12.0. Then, the product can be washed with water, filtrated and dried toobtain a complex hydroxide.

Analysis of Nickel Cobalt Complex Hydroxide

It is possible to confirm that a composition of the complex hydroxide isNi_(0.33)Co_(0.33)Mn_(0.33)W_(0.005)(OH)_(2+a), wherein 0≤a≤0.5 by thechemical analysis in a similar manner to that in Example 1.

A cross-section of the secondary particles of the nickel cobalt complexhydroxide is exposed in a similar condition to that in Example 1.

It is possible to confirm that the inside of the secondary particles isdense as exemplified in FIG. 21 by SEM observation of the cross-section.

It is possible to confirm a peak at the second layer from the obtainedCPS curve as exemplified in FIG. 22 by the line analysis with EDX in asimilar manner to that in Example 1.

It is possible to confirm that S1 and S2 satisfy an inequality ofS2>1.02 S1 from the CPS curve since S2 is 5.39 and S1 is 0.43.

It is possible to confirm that S2 and S3 satisfy an inequality ofS2>1.02 S3 from the CPS curve since S3 is 1.49.

Production of Positive Electrode Active Material

Preparation is carried out under a condition similar to that in Example1.

Analysis of Lithium Transition Metal Complex Oxide

It is possible to confirm that a composition of the lithium transitionmetal complex oxide is Li_(1.15)Ni_(0.33)Co_(0.33)Mn_(0.33)W_(0.005)O₂by the chemical analysis in a similar manner to that in Example 1.

A cross-section of the secondary particles of the lithium transitionmetal complex oxide is exposed under a condition similar to that inExample 1.

It is possible to confirm the secondary particles has a solid structureas exemplified in FIG. 23 by SEM observation of the cross-section.

It is possible to confirm a peak at the second layer from the obtainedCPS curve as exemplified in FIG. 24 by the line analysis with EDX in asimilar manner to that in Example 1.

It is possible to confirm that S4 and S5 satisfy an inequality ofS5>1.02 S4 from the CPS curve of the complex oxide since S5 is 2.65 andS4 is 0.18.

It is possible to confirm that S5 and S6 satisfy an inequality ofS5>1.02 S6 from the CPS curve of the complex oxide since S6 is 2.10.

Example 4 Production of Nickel Cobalt Complex Hydroxide

A complex hydroxide is prepared in a manner shown below.

Forming Seed Crystals

The step of forming seed crystals is carried out under a conditionsimilar to that in Example 1 except that the mixed solution containing anickel sulfate solution, a cobalt sulfate solution and a manganesesulfate solution in a molar ratio of 6:2:2 is prepared.

First Crystallization

A temperature within the vessel is maintained to 25° C. or more untilthe step of forming seed crystals is completed. The mixed solution in anamount corresponding to the solute of 660 mol and aqueous ammonia areadded simultaneously to the reaction vessel to the reaction vessel suchthat the ammonium ion concentration in the solution is 2000 ppm or moreto carry out the step of first crystallization while supplying a sodiumhydroxide solution to control pH value in the reaction solution to arange of from 9.5 to 12.0.

Second Crystallization

After the step of first crystallization, the temperature within thevessel is maintained to 25° C. or more. The mixed solution in an amountcorresponding to the solute of 540 mol, an ammonium tungstate solutioncontaining tungsten equivalent to 12 mol and aqueous ammonia are addedsimultaneously to the reaction vessel such that the ammonium ionconcentration in the solution is 2000 ppm or more to carry out the stepof second crystallization while supplying a sodium hydroxide solution tocontrol pH value in the reaction solution to a range of from 9.5 to12.0. Then, the product can be washed with water, filtrated and dried toobtain a complex hydroxide.

Analysis of Nickel Cobalt Complex Hydroxide

It is possible to confirm that a composition of the complex hydroxide isNi_(0.33)Co_(0.33)Mn_(0.33)W_(0.01)(OH)_(2+a), wherein 0≤a≤0.5 by thechemical analysis in a similar manner to that in Example 1.

A cross-section of the secondary particles of the nickel cobalt complexhydroxide is exposed in a similar condition to that in Example 1.

It is possible to confirm that the inside of the secondary particles isdense as exemplified in FIG. 25 by SEM observation of the cross-section.

It is possible to confirm a peak at the second layer from the obtainedCPS curve as exemplified in FIG. 26 by the line analysis of thecross-section with the energy dispersive X-ray analyzer EDX.

It is possible to confirm that S1 and S2 satisfy an inequality ofS2>1.02 S1 from the CPS curve since S2 is 2.25 and S1 is 0.88.

It is possible to confirm that S2 and S3 satisfy an inequality ofS2>1.02 S3 from the CPS curve since S3 is 0.

Production of Positive Electrode Active Material

Preparation is carried out under a condition similar to that in Example1.

Analysis of Lithium Transition Metal Complex Oxide

It is possible to confirm that a composition of the lithium transitionmetal complex oxide is Li_(1.15)Ni_(0.33)Co_(0.33)Mn_(0.33)W_(0.01)O₂ bythe chemical analysis in a similar manner to that in Example 1.

A cross-section of the secondary particles of the lithium transitionmetal complex oxide is exposed under a condition similar to that inExample 1.

It is possible to confirm the secondary particles have a solid structureas exemplified in FIG. 27 by SEM observation of the cross-section.

It is possible to confirm a peak at the second layer from the obtainedCPS curve of the complex oxide as exemplified in FIG. 28 by the lineanalysis of the cross-section with the energy dispersive X-ray analyzerEDX.

It is possible to confirm that S4 and S5 satisfy an inequality ofS5>1.02 S4 from the CPS curve of the complex oxide since S5 is 3.17 andS4 is 1.69.

It is possible to confirm that S2 and S3 satisfy an inequality ofS2>1.02 S3 from the CPS curve since S6 is 1.74.

Comparative Example 3 Production of Nickel Cobalt Complex Hydroxide

A complex hydroxide is prepared in a manner shown below.

Forming Seed Crystals

The step of forming seed crystals is carried out under a conditionsimilar to that in Comparative Example 1 except that the mixed solutioncontaining a nickel sulfate solution, a cobalt sulfate solution and amanganese sulfate solution in a molar ratio of 6:2:2 is prepared.

First Crystallization

Preparation is carried out under a condition similar to that inComparative Example 2.

Second Crystallization

Preparation is carried out under a condition similar to that inComparative Example 2.

Analysis of Nickel Cobalt Complex Hydroxide

It is possible to confirm that a composition of the complex hydroxide isNi_(0.33)Co_(0.33)Mn_(0.33)W_(0.01)(OH)_(2+a), wherein 0≤a≤0.5 by thechemical analysis in a similar manner to that in Example 1.

A cross-section of the secondary particles of the nickel cobalt complexhydroxide is exposed in a similar condition to that in Example 1.

It is possible to confirm that the inside of the secondary particles isdense as exemplified in FIG. 29 by SEM observation of the cross-section.

It is possible to confirm a peak at the third layer from the obtainedCPS curve as exemplified in FIG. 30 by the line analysis of thecross-section with the energy dispersive X-ray analyzer EDX.

It is possible to confirm that S1 and S2 satisfy an inequality ofS2>1.02 S1 from the CPS curve since S2 is 2.52 and S1 is 1.35.

It is possible to confirm that S2 and S3 satisfy an inequality of S3>S2from the CPS curve since S3 is 2.96.

Production of Positive Electrode Active Material

Preparation is carried out under a condition similar to that in Example1.

Analysis of Lithium Transition Metal Complex Oxide

It is possible to confirm that a composition of the lithium transitionmetal complex oxide is Li_(1.15)Ni_(0.33)Co_(0.33)Mn_(0.33)W_(0.01)O₂ bythe chemical analysis in a similar manner to that in Example 1.

A cross-section of the secondary particles of the lithium transitionmetal complex oxide is exposed under a condition similar to that inExample 1.

It is possible to confirm the secondary particles have a solid structureas exemplified in FIG. 31 by SEM observation of the cross-section.

It is possible to confirm a peak at the third layer from the obtainedCPS curve of the complex oxide as exemplified in FIG. 32 by the lineanalysis of the cross-section with the energy dispersive X-ray analyzerEDX.

It is possible to confirm that S4 and S5 satisfy an inequality ofS5>1.02 S4 from the CPS curve of the complex oxide since S5 is 3.12 andS4 is 0.52.

It is possible to confirm that S5 and S6 satisfy an inequality of S6>S5from the CPS curve of the complex oxide since S6 is 3.18.

Preparation of Secondary Battery

A secondary battery for evaluation is prepared in a manner shown below.

Non-Aqueous Electrolytic Solution Secondary Battery

A non-aqueous electrolytic solution secondary battery is prepared by thefollowing procedures.

Preparation of Positive Electrode

85 parts by weight of a positive electrode active material, 10 parts byweight of acetylene black and 5.0 parts by weight of PVDF(polyvinylidene fluoride) were dispersed in NMP (N-methyl-2-pyrrolidone)to prepare positive electrode slurry. The obtained positive electrodeslurry is applied to an aluminum foil, dried, and then,compression-molded with a roll press machine and cut off into apredetermined size to obtain a positive electrode.

Preparation of Negative Electrode

97.5 parts by weight of artificial graphite, 1.5 parts by weight of CMC(carboxymethyl cellulose) and 1.0 parts by weight of SBR(styrene-butadiene rubber) were dispersed in water to prepare negativeelectrode slurry. The obtained negative electrode slurry is applied to acopper foil, dried, and then, compression-molded with the roll pressmachine and cut off into a predetermined size to obtain a negativeelectrode.

Preparation of Non-Aqueous Electrolytic Solution

EC (ethylene carbonate) and MEC (methyl ethyl carbonate) were mixed at avolume ratio of 3:7 to be a solvent. Lithium hexafluorophosphate (LiPF₆)is dissolved into the obtained mixed solvent such that its concentrationis 1 mol/L to obtain a non-aqueous electrolytic solution.

Assembling Battery for Evaluation

Leading electrodes were respectively fixed to current collectors of thepositive electrode and the negative electrode, and then, they werevacuum-dried at 120° C. Subsequently, a separator made of porouspolyethylene was arranged between the positive electrode and thenegative electrode, and they were put in a bag-shaped laminated pack.After that, they were vacuum-dried at 60° C. to remove moisture adsorbedto each member. After vacuum-drying, the above-mentioned non-aqueouselectrolytic solution is poured into the laminated pack, and thelaminated pack is sealed to obtain a laminate-type non-aqueouselectrolytic solution secondary battery.

Solid Electrolyte Secondary Battery

A solid electrolyte secondary battery is prepared by the followingprocedures.

Preparation of Solid Electrolyte

Lithium sulfide and phosphorus pentasulfide are weighed under an argonatmosphere such that its molar ratio is 7:3. The weighed substances arepulverized and mixed by use of an agate mortar to obtain a sulfideglass. This is used as a solid electrolyte.

Preparation of Positive Electrode

60 parts by weight of the positive electrode active material, 36 partsby weight of the solid electrolyte and 4 parts by weight of VGCF(vapor-grown carbon fiber) are mixed to obtain a positive electrodemixed material.

Preparation of Negative Electrode

An indium foil having a thickness of 0.05 mm is cut out in a circularshape having a diameter of 11.00 mm to be a negative electrode.

Assembling Battery for Evaluation

A columnar lower mold having an outer diameter of 11.00 mm is insertedinto a cylindrical external mold having an inner diameter of 11.00 mmfrom the bottom of the external mold. Upper end of the lower mold isfixed at an intermediate position of the external mold. In this state,80 mg of the solid electrolyte is put from the upper side of theexternal mold onto the upper end of the lower mold. After that, acolumnar upper mold having an outer diameter of 11.00 mm is insertedfrom the upper side of the external mold. After insertion, pressure of90 MPa was applied from the upper side the upper mold to mold the solidelectrolyte into a solid electrolyte layer. After molding, the uppermold is pulled out from the upper side of the external mold, and 20 mgof the positive electrode mixed material is put from the upper side ofthe external mold onto the upper side of the solid electrolyte layer.After that, the upper mold is inserted again, and pressure of 360 MPa isapplied in turn to mold the positive electrode mixed material into apositive electrode layer. After molding, the upper mold is fixed, andthe fixing of the lower mold is released and pulled out from the lowerside of the external mold. Then, the negative electrode is put from thelower side of the lower mold onto the lower side of the solidelectrolyte layer. After that, the lower mold is inserted again, andpressure of 150 MPa is applied from the lower side of the lower mold tomold the negative electrode into a negative electrode layer. The lowermold is fixed under pressure. Then, the positive electrode terminal isfixed to the upper mold, and the negative electrode terminal is fixed tothe lower mold to obtain an all-solid-state secondary battery.

Evaluation of Battery Characteristics

Battery characteristics are evaluated in a manner shown below by use ofthe secondary batteries for evaluation.

Non-Aqueous Electrolytic Solution Secondary Battery

Hereinafter, DC-IR is measured for Example 1 and Comparative Examples 1and 2.

DC-IR

Aging was carried out by applying weak current to the non-aqueouselectrolytic solution secondary battery to allow the electrolyte tosufficiently sink into the positive electrode and the negativeelectrode. Subsequently, discharging with high current and charging withweak current were repeated. Charging capacity at tenth charging isdefined as total charging capacity of a battery. After eleventhdischarging, charging is carried out to 40% of the total chargingcapacity. After eleventh charging, the battery is put into athermostatic chamber in which the temperature is set to −25° C., andleft for 6 hours. Subsequently, discharging is carried out at adischarge current of 0.02 A, 0.04 A, 0.06 A to measure a voltage duringeach discharging. Current and the value of the voltage during thedischarging are plotted on the horizontal axis and the vertical axis,respectively, and an absolute value of an inclination of the obtainedcurrent-voltage plot is determined within a range where the plot is keptlinear to be a resistance R of the battery (−25° C.). Lower value of R(−25° C.) means higher low-temperature output power characteristics.

Solid Electrolyte Secondary Battery

Following characteristics are measured for Example 1 and ComparativeExamples 2 and 3.

Initial Charge-Discharge Characteristics

Constant-current/constant voltage charging was carried out at currentdensity of 0.195 μA/cm² and charging voltage of 4.0 V. After charging,constant-current discharging is carried out at current density of 0.195μA/cm² and discharging voltage of 1.9 V to determine a dischargecapacity Q_(d).

Table 1 shows the results of the ratio of MOL(1) in the step of firstcrystallization to the total of molar amounts MOL(1) in the step offirst crystallization and MOL(2) in the step of second crystallization,low-temperature output power characteristics of the non-aqueouselectrolytic solution secondary battery and the discharge capacity ofthe solid electrolyte secondary battery.

The results of SEM-EDX peaks of the lithium transition metal complexoxides from the nickel cobalt complex oxide particles in Examples 1 to4, Comparative Examples 1 to 3 are shown in FIGS. 8, 12, 16, 20, 24, 28,32.

TABLE 1 M(1)/ DC-IR Qd [M(1) + M(2)] Ω mAh/g Example 1 0.64 11.7 112Example 2 0.5 11.8 101 Example 3 0.92 11.7 104 Example 4 0.55 10.4Comparative 0 12.5 98 Example 1 Comparative 0.17 12.8 100 Example 2Comparative 0.17 12.5 Example 3

The following matters can be seen from Table 1 and FIGS. 8, 12, 16, 20,24, 28, 32. It can be said that the non-aqueous electrolytic solutionsecondary batteries according to Examples 1 to 4 where the lithiumtransition metal complex oxide having a peak at the second layer asshown in FIG. 8 is used as a positive electrode active material hasimproved low-temperature output power characteristics compared toComparative Examples 1 to 3. In addition, it can be said that the solidelectrolyte secondary battery has increased discharge capacity comparedto Comparative Examples 1 and 2. It is considered that these are becausean interfacial resistance between the positive electrode active materialand the solid electrolyte is decreased, resulting in suppressed voltagedrop inside the battery.

INDUSTRIAL APPLICABILITY

The non-aqueous electrolytic solution secondary battery in which thepositive electrode active material obtained by the production methodaccording to the present disclosure is used for the positive electrodehas excellent output power characteristics, and can be used suitably asa power source for electric equipment, electric vehicle and the like. Inaddition, the solid electrolyte secondary battery in which the positiveelectrode active material obtained by the production method according tothe present disclosure is used for the positive electrode has excellentdischarge capacity, and can be used suitably as a power source for anelectric apparatus such as standby power supply for a power plant whichrequires high output power in thermally and mechanically harshenvironment since it does not comprise a non-aqueous electrolyticsolution.

It is to be understood that although the present invention has beendescribed with regard to preferred embodiments thereof, various otherembodiments and variants may occur to those skilled in the art, whichare within the scope and spirit of the invention, and such otherembodiments and variants are intended to be covered by the followingclaims.

DENOTATION OF REFERENCE NUMERAL

-   -   1 Starting point for measuring secondary particles

1. A nickel cobalt complex hydroxide represented by a formula:Ni_(1-x-y)Co_(x)Mn_(y)M_(z)(OH)_(2+a), wherein 0.10≤x≤0.35, 0≤y≤0.35,0<z≤0.05, 0≤a≤0.5, M is at least one element selected from a groupconsisting of Al, Mg, Ca, Ti, Zr, Nb, Ta, Cr, Mo, W, Fe, Cu, Si, Sn, Bi,Ga, Y, Sm, Er, Ce, Nd, La, Cd and Lu, wherein the nickel cobalt complexhydroxide is in a form of secondary particles formed by agglomeration ofprimary particles, wherein the secondary particles comprises: a firstlayer having a radial depth ratio of less than 5% from a surface in thesecondary particles; a second layer having a radial depth ratio in arange of 5% to less than 50% and located at an inner side than the firstlayer in the secondary particles; and a third layer having a radialdepth ratio of 50% or greater and located at an inner side than thesecond layer in the secondary particles, and wherein a SEM-EDX spectrumof said element M with respect to the radial depth in the secondaryparticles have a peak in the second layer.
 2. The nickel cobalt complexhydroxide according to claim 1, wherein assuming that the amount of saidelement M in the first layer is S1 and that the amount of said element Min the second layer is S2, S1 and S2 satisfy an inequality of S2>1.02Si.
 3. The nickel cobalt complex hydroxide according to claim 2, whereinassuming that the amount of said element M in the third layer is S3, S2and S3 satisfy an inequality of S2>1.02 S3.
 4. The nickel cobalt complexhydroxide according to claim 1, wherein the secondary particles of thenickel cobalt complex hydroxide have an inner core part made of fineprimary particles, and the secondary particles comprise plate-like orneedle-like primary particles larger than the fine primary particlesoutside the inner core part.
 5. The nickel cobalt complex hydroxideaccording to claim 1, wherein the secondary particles of the nickelcobalt complex hydroxide are made of rod-like or plate-like primaryparticles.
 6. A positive electrode active material for non-aqueouselectrolyte secondary battery comprising a lithium transition metalcomplex oxide represented by a formula:Li_(a)Ni_(1-x-y)Co_(x)Mn_(y)M_(z)O₂, wherein 0.955≤a≤1.2, 0.10≤x≤0.35,0≤y≤0.35, 0<z≤0.05, M is at least one element selected from a groupconsisting of Al, Mg, Ca, Ti, Zr, Nb, Ta, Cr, Mo, W, Fe, Cu, Si, Sn, Bi,Ga, Y, Sm, Er, Ce, Nd, La, Cd and Lu, wherein the lithium transitionmetal complex oxide is in a form of secondary particles formed byagglomeration of primary particles, wherein the secondary particlescomprise: a first layer having a radial depth ratio of less than 5% froma surface in the secondary particle; a second layer having a radialdepth ratio in a range of 5% to less than 50% and located at an innerside than the first layer in the secondary particles; and a third layerhaving a radial depth ratio of 50% or greater and located at an innerside than the second layer in the secondary particles, and wherein aSEM-EDX spectrum of said element M with respect to the radial depth ofthe secondary particles have a peak in the second layer.
 7. The positiveelectrode active material for non-aqueous electrolyte secondary batteryaccording to claim 6, wherein assuming that the amount of said element Min the first layer is S4 and that the amount of said element M in thesecond layer is S5, S4 and S5 satisfy an inequality of S5>1.02 S4. 8.The positive electrode active material for non-aqueous electrolytesecondary battery according to claim 7, wherein assuming that the amountof said element M in the third layer is S6, S5 and S6 satisfy aninequality of S5>1.02 S6.
 9. The positive electrode active material fornon-aqueous electrolyte secondary battery according to claim 6, whereinthe secondary particles of the lithium transition metal complex oxideare hollow inner side of the second layer.
 10. The positive electrodeactive material for non-aqueous electrolyte secondary battery accordingto claim 6, wherein the secondary particles of the lithium transitionmetal complex oxide are solid inside.
 11. A non-aqueous electrolyticsolution secondary battery comprising a positive electrode, a negativeelectrode, a separator and a non-aqueous electrolytic solution, whereinthe positive electrode comprises the positive electrode active materialfor non-aqueous electrolyte secondary battery according to claim
 6. 12.A solid electrolyte secondary battery comprising a positive electrode, anegative electrode and a solid electrolyte, wherein the positiveelectrode comprises the positive electrode active material fornon-aqueous electrolyte secondary battery according to claim 6.